Organic electroluminescent device and platinum compound

ABSTRACT

An organic electroluminescent device, which has a pair of electrodes, and at least one organic layer including a luminescent layer between the electrodes, wherein the organic layer contains at least one compound of formula (1): 
     
       
         
         
             
             
         
       
     
     wherein Q 11  are atoms for forming a nitrogen-containing hetero ring; Z 11  to Z 13  each independently represents CR, wherein R represents a substituent, CH or N; n 11  is 0 or 1; M 11  is a metal or boron ion that may further have a ligand(s); and a compound of formula (6): 
     
       
         
         
             
             
         
       
     
     wherein R 63  to R 66  each is a hydrogen atom or a substituent; X 61  to X 64  and Z 61  to Z 66  each is CR, wherein R represents a substituent, CH or N.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of U.S. application Ser. No. 12/571,093filed Sep. 30, 2009, which is a Divisional of U.S. application Ser. No.10/548,669 filed Sep. 9, 2005, now U.S. Pat. No. 7,615,633, which is a371 of PCT/JP2004/006498 filed May 7, 2004, which claims benefit of JPANo. 2003-132257 filed May 9, 2003 and JPA No. 2004-88575 filed Mar. 25,2004. The above-noted applications are incorporated herein by referencein their entirety.

TECHNICAL FIELD

The present invention relates to a luminescent device, particularly anorganic electroluminescent device (hereinafter sometimes referred to asan EL device), and to a platinum compound that is useful in theluminescent device.

BACKGROUND ART

Recently, a variety of types of display devices are actively researchedand developed. Among these, much attention is focused on organicelectroluminescent (EL) devices. This is because organic EL devices arepromising display devices capable of emitting light of high luminanceunder low applied voltage. An important characteristic of organic ELdevices is life (durability), and as such, studies have been made towardfurther prolonging the life of organic EL devices. As a means to prolonglife, luminescent devices of a type comprising a hole-injection layercontaining CuPc (copper phthalocyanine) are known (as described, forexample, in JP-A-57-51781 (“JP-A” means unexamined published Japanesepatent application) and Applied Physics Letters, 15, 69, 1996). However,such luminescent devices are still low in quantum efficiency.Accordingly, there is a demand for further improved devices.

On the other hand, for the development of organic EL devices in recentyears, various studies have aimed at improving the external quantumefficiency of the devices. In particular, observation is focused onluminescent devices containing a phosphorescent material, such astris-phenylpyridine iridium complexes (see WO 00/070655) andtetradentate platinum complexes (for example, octaethylporphyrinplatinum complexes) (see U.S. Pat. No. 6,303,238 B1 and No. 6,653,564B1), because high-external quantum efficiency is attained with thesedevices. However, these phosphorescent materials and devices containingthe phosphorescent material have needed life prolongation. In addition,conventional tetradentate platinum complexes (see U.S. Pat. No.6,303,238 B1 and No. 6,653,564 B1) have the problem that light emissionis restricted to the color ranging from orange to red, and therefore itis difficult to obtain light emission in the short wavelength rangingfrom blue to green that is necessary for use in full color displays andmulticolor displays.

DISCLOSURE OF THE INVENTION

According to the present invention, there are provided the followingmeans:

(1) An organic electroluminescent device, comprising a pair ofelectrodes, and at least one organic layer including a luminescent layerbetween the electrodes, wherein said organic layer comprises at leastone compound represented by formula (1):

wherein, in formula (1), Q¹¹ represents a group of atoms for forming anitrogen-containing hetero ring; Z¹¹, Z¹² and Z¹³ each represent asubstituted or unsubstituted carbon atom or nitrogen atom; n¹¹represents 0 or 1; M¹¹ represents a metal ion or a boron ion, each ofwhich may further have a ligand(s).

(2) The organic electroluminescent device as described in the item (1),wherein the compound represented by formula (1) is a compoundrepresented by formula (11):

wherein, in formula (11), Z¹⁰¹, Z¹⁰² and Z¹⁰³ each represent asubstituted or unsubstituted carbon atom or nitrogen atom; L¹⁰¹, L¹⁰²,L¹⁰³ and L¹⁰⁴ each represent a single bond or a linking group; Q¹⁰¹ andQ¹⁰³ each represent a group containing a carbon, nitrogen, phosphorus,oxygen or sulfur atom as a coordinating atom to M¹⁰¹ respectively; Q¹⁰²represents a group containing a nitrogen, phosphorus, oxygen or sulfuratom as a coordinating atom to M¹⁰¹; and M¹⁰¹ represents a metal ionthat may further have a ligand(s).

(3) The organic electroluminescent device as described in the item (1),wherein the compound represented by formula (1) is a compoundrepresented by formula (15):

wherein, in formula (15), Z⁵⁰¹, Z⁵⁰² and Z⁵⁰³ each represent asubstituted or unsubstituted carbon atom or nitrogen atom; L⁵⁰¹, L⁵⁰²,L⁵⁰³ and L⁵⁰⁴ each represent a single bond or a linking group; Q⁵⁰¹ andQ⁵⁰² each represent a group containing a carbon, nitrogen, phosphorus,oxygen or sulfur atom as a coordinating atom to M⁵⁰¹ respectively; Q⁵⁰³represents a group containing a nitrogen, phosphorus, oxygen or sulfuratom as a coordinating atom to M⁵⁰¹; and M⁵⁰¹ represents a metal ionthat may further have a ligand(s).

(4) The organic electroluminescent device as described in the item (2),wherein the compound represented by formula (11) is a compoundrepresented by formula (2) or (3):

wherein, in formula (2), Q²¹ and Q²² each represent a group for forminga nitrogen-containing hetero ring; X²¹, X²², X²³ and X²⁴ each representa substituted or unsubstituted carbon atom or nitrogen atom; Z²¹, Z²²,Z²³, Z²⁴, Z²⁵, and Z²⁶ each represent a substituted or unsubstitutedcarbon atom or nitrogen atom; M²¹ represents a metal ion that mayfurther have a ligand(s);

wherein, in formula (3), R³¹ and R³² each represent a hydrogen atom or asubstituent; Q³¹ and Q³² each represent a group for forming anitrogen-containing hetero ring; X³¹, X³², X³³ and X³⁴ each represent asubstituted or unsubstituted carbon atom or nitrogen atom; Z³¹, Z³²,Z³³, Z³⁴, Z³⁵, and Z³⁶ each represent a substituted or unsubstitutedcarbon atom or nitrogen atom.

(5) The organic electroluminescent device as described in the item (4),wherein the compound represented by formula (2) is a compoundrepresented by formula (4):

wherein, in formula (4), R⁴³, R⁴⁴, R⁴⁵ and R⁴⁶ each represent a hydrogenatom or a substituent; X⁴¹, X⁴², X⁴³ and X⁴⁴ each represent asubstituted or unsubstituted carbon atom or nitrogen atom; Z⁴¹, Z⁴²,Z⁴³, Z⁴⁴, Z⁴⁵ and Z⁴⁶ each represent a substituted or unsubstitutedcarbon atom or nitrogen atom; M⁴¹ represents a metal ion that mayfurther have a ligand(s).

(6) The organic electroluminescent device as described in the item (4),wherein the compound represented by formula (3) is a compoundrepresented by formula (5):

wherein, in formula (5), R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵ and R⁵⁶ each representa hydrogen atom or a substituent; X⁵¹, X⁵², X⁵³ and X⁵⁴ each represent asubstituted or unsubstituted carbon atom or nitrogen atom; Z⁵¹, Z⁵²,Z⁵³, Z⁵⁴, Z⁵⁵ and Z⁵⁶ each represent a substituted or unsubstitutedcarbon atom or nitrogen atom.

(7) The organic electroluminescent device as described in the item (2),wherein the compound represented by formula (11) is a compoundrepresented by formula (12) or a tautomer thereof:

wherein, in formula (12), Z²⁰¹, Z²⁰², Z²⁰³, Z²⁰⁴, Z²⁰⁵, Z²⁰⁶, Z²⁰⁷,Z²⁰⁸, Z²⁰⁹, Z²¹⁰, Z²¹¹, and Z²¹² each represent a substituted orunsubstituted carbon atom or nitrogen atom; L²⁰¹, L²⁰², L²⁰³ and L²⁰⁴each represent a single bond or a linking group; and M²⁰¹ represents ametal ion that may further have a ligand(s).

(8) The organic electroluminescent device as described in the item (2),wherein the compound represented by formula (11) is a compoundrepresented by formula (13) or a tautomer thereof:

wherein, in formula (13), Z³⁰¹, Z³⁰², Z³⁰³, Z³⁰⁴, Z³⁰⁵, Z³⁰⁶, Z³⁰⁷,Z³⁰⁸, Z³⁰⁹, and Z³¹⁰ each represent a substituted or unsubstitutedcarbon atom or nitrogen atom; L³⁰¹, L³⁰², L³⁰³ and L³⁰⁴ each represent asingle bond or a linking group; and M³⁰¹ represents a metal ion that mayfurther have a ligand(s).

(9) The organic electroluminescent device as described in the item (2),wherein the compound represented by formula (11) is a compoundrepresented by formula (14) or a tautomer thereof:

wherein, in formula (14), Z⁴⁰¹, Z⁴⁰², Z⁴⁰³, Z⁴⁰⁴, Z⁴⁰⁵, Z⁴⁰⁶, Z⁴⁰⁷,Z⁴⁰⁸, Z⁴⁰⁹, Z⁴¹⁰, Z⁴¹¹, and Z⁴¹² each represent a substituted orunsubstituted carbon atom or nitrogen atom; L⁴⁰¹, L⁴⁰², L⁴⁰³ and L⁴⁰⁴each represent a single bond or a linking group; M⁴⁰¹ represents a metalion that may further have a ligand(s); and X⁴⁰¹ and X⁴⁰² each representan oxygen atom, a substituted or unsubstituted nitrogen atom, or asulfur atom.

(10) The organic electroluminescent device as described in the item (3),wherein the compound represented by formula (15) is a compoundrepresented by formula (16) or a tautomer thereof:

wherein, in formula (16), Z⁶⁰¹, Z⁶⁰², Z⁶⁰³, Z⁶⁰⁴, Z⁶⁰⁵, Z⁶⁰⁶, Z⁶⁰⁷,Z⁶⁰⁸, Z⁶⁰⁹, Z⁶¹⁰, Z⁶¹¹, and Z⁶¹² each represent a substituted orunsubstituted carbon atom or nitrogen atom; L⁶⁰¹, L⁶⁰², L⁶⁰³ and L⁶⁰⁴each represent a single bond or a linking group; and M⁶⁰¹ represents ametal ion that may further have a ligand(s).

(11) The organic electroluminescent device as described in the item (3),wherein the compound represented by formula (15) is a compoundrepresented by formula (17) or a tautomer thereof:

wherein, in formula (17), Z⁷⁰¹, Z⁷⁰², Z⁷⁰³, Z⁷⁰⁴, Z⁷⁰⁵, Z⁷⁰⁶, Z⁷⁰⁷,Z⁷⁰⁸, Z⁷⁰⁹, and Z⁷¹⁰ each represent a substituted or unsubstitutedcarbon atom or nitrogen atom; L⁷⁰¹, L⁷⁰², L⁷⁰³ and L⁷⁰⁴ each represent asingle bond or a linking group; and M⁷⁰¹ represents a metal ion that mayfurther have a ligand(s).

(12) The organic electroluminescent device as described in the item (3),wherein the compound represented by formula (15) is a compoundrepresented by formula (18) or a tautomer thereof:

wherein, in formula (18), Z⁸⁰¹, Z⁸⁰², Z⁸⁰³, Z⁸⁰⁴, Z⁸⁰⁵, Z⁸⁰⁶, Z⁸⁰⁷,Z⁸⁰⁸, Z⁸⁰⁹, Z⁸¹⁰, Z⁸¹¹, and Z⁸¹² each represent a substituted orunsubstituted carbon atom or nitrogen atom; L⁸⁰¹, L⁸⁰², L⁸⁰³ and L⁸⁰⁴each represent a single bond or a linking group; M⁸⁰¹ represents a metalion that may further have a ligand(s); and X⁸⁰¹ and X⁸⁰² each representan oxygen atom, a substituted or unsubstituted nitrogen atom, or asulfur atom.

(13) The organic electroluminescent device as described in any one ofthe items (1) to (12), wherein the organic layer is at least one of aluminescent layer and a positive hole-injection layer.(14) A compound represented by formula (6):

wherein, in formula (6), R⁶³, R⁶⁴, R⁶⁵ and R⁶⁶ each represent a hydrogenatom or a substituent; X⁶¹, X⁶², X⁶³ and X⁶⁴ each represent asubstituted or unsubstituted carbon atom or nitrogen atom; Z⁶¹, Z⁶²,Z⁶³, Z⁶⁴, Z⁶⁵ and Z⁶⁶ each represent a substituted or unsubstitutedcarbon atom or nitrogen atom.

(15) The organic electroluminescent device as described in any one ofthe items (1) to (13), wherein the compound represented by any offormulae (1) to (17) emits a phosphorescence.(16) The organic electroluminescent device as described in any one ofthe items (1) to (13) and (15), wherein the luminescent (light-emitting)layer contains at least one host material, and at least one of thecompounds represented by any of formulae (1) to (13).(17) The organic electroluminescent device as described in the item(16), wherein the host material in the light-emitting layer is acomplex.(18) The organic electroluminescent device as described in the item (16)or (17), wherein the light-emitting layer contains at least two hostmaterials.

Other and further features and advantages of the invention will appearmore fully from the following description.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail below.

First, the compound represented by formula (1) will be described.

Q¹¹ represents a group of atoms that form a nitrogen-containing heteroring, together with two carbon atoms bonding to the Q¹¹ and a nitrogenatom directly bonding to the carbon atoms. The number of ring member ofthe nitrogen-containing hetero ring formed by Q¹¹ is not particularlylimited, but preferably in the range of 12 to 20, more preferably in therange of 14 to 16, and further more preferably 16. Z¹¹, Z¹² and Z¹³ eachrepresent a substituted or unsubstituted carbon atom or nitrogen atom.As a combination of Z¹¹, Z¹² and Z¹³, it is preferable that at least oneof Z¹¹, Z¹² and Z¹³ is a nitrogen atom. Examples of the substituent onthe carbon atom include an alkyl group (preferably having 1 to 30 carbonatoms, more preferably having 1 to 20 carbon atoms, and particularlypreferably having 1 to 10 carbon atoms, e.g., methyl, ethyl, iso-propyl,tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl,cyclohexyl), an alkenyl group (preferably having 2 to 30 carbon atoms,more preferably having 2 to 20 carbon atoms, and particularly preferablyhaving 2 to 10 carbon atoms, e.g., vinyl, allyl, 2-butenyl, 3-pentenyl),an alkynyl group (preferably having 2 to 30 carbon atoms, morepreferably having 2 to 20 carbon atoms, and particularly preferablyhaving 2 to 10 carbon atoms, e.g., propargyl, 3-pentynyl), an aryl group(preferably having 6 to 30 carbon atoms, more preferably having 6 to 20carbon atoms, and particularly preferably having 6 to 12 carbon atoms,e.g., phenyl, p-methylphenyl, naphthyl, anthranyl), an amino group(preferably having 0 to 30 carbon atoms, more preferably having 0 to 20carbon atoms, and particularly preferably having 0 to 10 carbon atoms,e.g., amino, methylamino, dimethylamino, diethylamino, dibenzylamino,diphenylamino, ditolylamino), an alkoxy group (preferably having 1 to 30carbon atoms, more preferably having 1 to 20 carbon atoms, andparticularly preferably having 1 to 10 carbon atoms, e.g., methoxy,ethoxy, butoxy, 2-ethylhexyloxy), an aryloxy group (preferably having 6to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, andparticularly preferably having 6 to 12 carbon atoms, e.g., phenyloxy,1-naphthyloxy, 2-naphthyloxy), a hetero ring oxy group (preferablyhaving 1 to 30 carbon atoms, more preferably having 1 to 20 carbonatoms, and particularly preferably having 1 to 12 carbon atoms, e.g.,pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy), an acyl group(preferably having 1 to 30 carbon atoms, more preferably having 1 to 20carbon atoms, and particularly preferably having 1 to 12 carbon atoms,e.g., acetyl, benzoyl, formyl, pivaloyl), an alkoxycarbonyl group(preferably having 2 to 30 carbon atoms, more preferably having 2 to 20carbon atoms, and particularly preferably having 2 to 12 carbon atoms,e.g., methoxycarbonyl, ethoxycarbonyl), an aryloxycarbonyl group(preferably having 7 to 30 carbon atoms, more preferably having 7 to 20carbon atoms, and particularly preferably having 7 to 12 carbon atoms,e.g., phenyloxycarbonyl), an acyloxy group (preferably having 2 to 30carbon atoms, more preferably having 2 to 20 carbon atoms, andparticularly preferably having 2 to 10 carbon atoms, e.g., acetoxy,benzoyloxy), an acylamino group (preferably having 2 to 30 carbon atoms,more preferably having 2 to 20 carbon atoms, and particularly preferablyhaving 2 to 10 carbon atoms, e.g., acetylamino, benzoylamino), analkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, morepreferably having 2 to 20 carbon atoms, and particularly preferablyhaving 2 to 12 carbon atoms, e.g., methoxycarbonylamino), anaryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, morepreferably having 7 to 20 carbon atoms, and particularly preferablyhaving 7 to 12 carbon atoms, e.g., phenyloxycarbonylamino), asulfonylamino group (preferably having 1 to 30 carbon atoms, morepreferably having 1 to 20 carbon atoms, and particularly preferablyhaving 1 to 12 carbon atoms, e.g., methanesulfonylamino,benzenesulfonylamino), a sulfamoyl group (preferably having 0 to 30carbon atoms, more preferably having 0 to 20 carbon atoms, andparticularly preferably having 0 to 12 carbon atoms, e.g., sulfamoyl,methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl), a carbamoyl group(preferably having 1 to 30 carbon atoms, more preferably having 1 to 20carbon atoms, and particularly preferably having 1 to 12 carbon atoms,e.g., carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl), analkyl thio group (preferably having 1 to 30 carbon atoms, morepreferably having 1 to 20 carbon atoms, and particularly preferablyhaving 1 to 12 carbon atoms, e.g., methylthio, ethylthio), an aryl thiogroup (preferably having 6 to 30 carbon atoms, more preferably having 6to 20 carbon atoms, and particularly preferably having 6 to 12 carbonatoms, e.g., phenylthio), a hetero ring thio group (preferably having 1to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, andparticularly preferably having 1 to 12 carbon atoms, e.g., pyridyl thio,2-benzimidazolyl thio, 2-benzoxazoly thio, 2-benzthiazolyl thio), asulfonyl group (preferably having 1 to 30 carbon atoms, more preferablyhaving 1 to 20 carbon atoms, and particularly preferably having 1 to 12carbon atoms, e.g., mesyl, tosyl), a sulfinyl group (preferably having 1to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, andparticularly preferably having 1 to 12 carbon atoms, e.g.,methanesulfinyl, benzenesulfinyl), a ureido group (preferably having 1to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, andparticularly preferably having 1 to 12 carbon atoms, e.g., ureido,methylureido, phenylureido), a phosphoric acid amido group (preferablyhaving 1 to 30 carbon atoms, more preferably having 1 to 20 carbonatoms, and particularly preferably having 1 to 12 carbon atoms, e.g.,diethyl phosphoamido, phenyl phosphoamido), a hydroxyl group, a mercaptogroup, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), acyano group, a sulfo group, a carboxyl group, a nitro group, ahydroxamic acid group, a sulfino group, a hydrazino group, an iminogroup, a heterocyclic group (preferably having 1 to 30 carbon atoms,more preferably having 1 to carbon atoms, and containing a hetero atomsuch as nitrogen, oxygen and sulfur, preferably being a hetero arylgroup, specifically for example, imidazolyl, pyridyl, quinolyl, furyl,thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl,benzthiazolyl, carbazolyl, azepinyl), a silyl group (preferably having 3to 40 carbon atoms, more preferably having 3 to 30 carbon atoms, andparticularly preferably having 3 to 24 carbon atoms, e.g.,trimethylsilyl, triphenylsilyl), and a silyloxy group (preferably having3 to 40 carbon atoms; more preferably having 3 to 30 carbon atoms, andparticularly preferably having 3 to 24 carbon atoms, e.g.,trimethylsilyloxy, triphenylsilyloxy). These substituents may be furthersubstituted by, for example, aforementioned substituents on the carbonatom.

M¹¹ represents a metal ion or a boron ion, each of which may furtherhave a ligand(s), M¹¹ is preferably a metal ion that may further have aligand(s), and more preferably a metal ion having no additional ligand.The metal ion is not particularly limited, but divalent or trivalentmetal ions are preferable. As the divalent or trivalent metal ions, arepreferable cobalt, magnesium, zinc, palladium, nickel, copper, platinum,lead, aluminum, iridium, europium, rhenium, rhodium and ruthenium ions.Of these, are more preferable cobalt, magnesium, zinc, palladium,nickel, copper, platinum and lead ions, with copper and platinum ionsbeing further preferable. A platinum ion is particular preferable. Whenn¹¹ is 1, M¹¹ may or may not bond to an atom(s) being contained in Q¹¹,but it is preferable that M¹¹ bonds to the atom(s).

The aforementioned (additional) ligand that may be further opposed byM¹¹, is not particularly restricted, but it is preferably a monodentateor bidentate ligand, and more preferably a bidentate ligand. Thecoordinating atom is not particularly restricted, but it is preferablyoxygen, sulfur, nitrogen, carbon and phosphorus atoms, more preferablyoxygen, nitrogen and carbon atoms, and furthermore preferably oxygen andnitrogen atoms.

n¹¹ is preferably 0 or 1, more preferably 1.

The compounds represented by formula (1) are preferably thoserepresented by formula (2) or (3), or their tautomers (those representedby formula (2) or their tautomers are more preferable); furthermorepreferably the compounds represented by formula (4) or (5), or theirtautomers (those represented by formula (4) or their tautomers are morepreferable).

Further, as the compounds represented by formula (1), those representedby formula (11) or (15) are also preferable. As the compound representedby formula (11), there are preferably illustrated a compound representedby formula (12) or a tautomer thereof, a compound represented by formula(13) or a tautomer thereof, and a compound represented by formula (14)or a tautomer thereof; more preferably a compound represented by formula(12) or a tautomer thereof, and a compound represented by formula (13)or a tautomer thereof; and furthermore preferably a compound representedby formula (12) or a tautomer thereof.

As the compound represented by formulae (15), there are preferablyillustrated a compound represented by formula (16) or a tautomerthereof, a compound represented by formula (17) or a tautomer thereof,and a compound represented by formula (18) or a tautomer thereof; morepreferably a compound represented by formula (16) or a tautomer thereof,and a compound represented by formula (17) or a tautomer thereof; andfurthermore preferably a compound represented by formula (16) or atautomer thereof.

Next, the compound represented by formula (2) will be described.

Z²¹, Z²², Z²³, Z²⁴, Z²⁵, Z²⁶ and M²¹ have the same meanings as those ofthe aforementioned Z¹¹, Z¹², Z¹³, Z¹¹, Z¹², Z¹³ and M¹¹, respectively,with the same preferable ranges.

Q²¹ and Q²² each represent a group for forming nitrogen-containinghetero ring. The nitrogen-containing hetero rings formed by Q²¹ or Q²²are not particularly limited, but are preferably a pyrrole ring, animidazole ring, a triazole ring, a condensed ring containing at leastone of these rings (for example, benzopyrrole), and a tautomer thereof(for example, as described below, in formula (4), thenitrogen-containing 5-membered rings having R⁴³, R⁴⁴, R⁴⁵ and R⁴⁶ aredefined to be a tautomer of pyrrole), more preferably a pyrrole ring anda condensed ring containing a pyrrole ring (for example, benzopyrrole).

X²¹, X²², X²³ and X²⁴ each represent a substituted or unsubstitutedcarbon atom or nitrogen atom, preferably an unsubstituted carbon atom ornitrogen atom, and more preferably an unsubstituted nitrogen atom.

Next, the compound represented by formula (3) will be described.

Q³¹, Q³², Z³¹, Z³², Z³³, Z³⁴, Z³⁵, Z³⁶, X³¹, X³², X³³, and X³⁴ have thesame meanings as those of the aforementioned Q²¹, Q²², Z²¹, Z²², Z²³,Z²⁴, Z²⁵, Z²⁶, X²¹, X²², X²³, and X²⁴ in formula (2), respectively, withthe same preferable ranges.

R³¹ and R³² each represent a hydrogen atom or a substituent, with thehydrogen atom being preferable. As the substituent, there areillustrated, for example, an alkyl group, an alkenyl group, an arylgroup, a hetero aryl group, an acyl group (e.g., acetyl, benzoyl,trifluoroacetyl) and a sulfonyl group (e.g., methanesulfonyl,pentafluorobenzenesulfonyl), that are exemplified as examples of thesubstituent on the carbon atom, when Z¹¹, Z¹² or Z¹³ in theaforementioned formula (1) is a carbon atom. These substituents each mayfurther have a substituent(s) (for example, any of the aforementionedsubstituents on the carbon atom).

Next, the compound represented by formula (4) will be described.

Z⁴¹, Z⁴², Z⁴³, Z⁴⁴, Z⁴⁵, Z⁴⁶, X⁴¹, X⁴², X⁴³, X⁴⁴ and M⁴¹ have the samemeanings as those of the aforementioned Z²¹, Z²², Z²³, Z²⁴, Z²⁵, Z²⁶,X²¹, X²², X²³, X²⁴, and M²¹ in formula (2), respectively, with the samepreferable ranges.

R⁴³, R⁴⁴, R⁴⁵ and R⁴⁶ each represent a hydrogen atom or a substituent.As the substituent, there can be mentioned groups that are exemplifiedas the substituent on the carbon atom with respect to Z¹¹ or Z¹² in theaforementioned formula (1).

R⁴³, R⁴⁴, R⁴⁵ and R⁴⁶ each are preferably a hydrogen atom, or an alkylgroup or an aryl group that are exemplified as the substituent on Z¹¹ orZ¹² in the aforementioned formula (1), or a group that forms a ringstructure (e.g., a benzene-condensed ring, a pyridine-condensed ring)when R⁴³ and R⁴⁴ or R⁴⁵ and R⁴⁶ bond to each other; more preferably analkyl group, an aryl group, or a group that forms a ring structure(e.g., a benzene-condensed ring, a pyridine-condensed ring) when R⁴³ andR⁴⁴ or R⁴⁵ and R⁴⁶ bond to each other; and furthermore preferably agroup that forms a ring structure (e.g., a benzene-condensed ring, apyridine-condensed ring) when R⁴³ and R⁴⁴ or R⁴⁵ and R⁴⁶ bond to eachother.

Next, the compound represented by formula (5) will be described.

R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, Z⁵¹, Z⁵², Z⁵³, Z⁵⁴, Z⁵⁵, Z⁵⁶, X⁵¹, X⁵²,X⁵³, and X⁵⁴ have the same meanings as those of the aforementioned R³¹,R³², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, Z⁴¹, Z⁴², Z⁴³, Z⁴⁴, Z⁴⁵, Z⁴⁶, X⁴¹, X⁴¹, X⁴²,X⁴³, and X⁴⁴ in formulas (3) and (4), respectively, with the samepreferable ranges.

Next, the compound represented by formula (6) will be described.

R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, Z⁶¹, Z⁶², Z⁶³, Z⁶⁴, Z⁶⁵, Z⁶⁶, X⁶¹, X⁶², X⁶³, and X⁶⁴have the same meanings as those of the aforementioned R⁴³, R⁴⁴, R⁴⁵,R⁴⁶, Z⁴¹, Z⁴², Z⁴³, Z⁴⁴, Z⁴⁵, Z⁴⁶, X⁴¹, X⁴², X⁴³, and X⁴⁴ in formula(4), respectively, with the same preferable ranges.

Next, the compound represented by formula (11) will be described.

Z¹⁰¹, Z¹⁰² and Z¹⁰³ each represent a substituted or unsubstituted carbonatom or nitrogen atom. At least one of Z¹⁰¹, Z¹⁰² and Z¹⁰³ is preferablya nitrogen atom.

L¹⁰¹, L¹⁰², L¹⁰³ and L¹⁰⁴ each represent a single bond or a linkinggroup. The linking group is not particularly restricted. Examples of thelinking group include a carbonyl-linking group, an alkylene group, analkenylene group, an arylene group, a hetero arylene group, anitrogen-containing hetero ring-linking group, an oxygen atom-linkinggroup, an amino-linking group, an imino-linking group, and a combinationof at least two groups selected from these linking groups.

As the L¹⁰¹, L¹⁰², L¹⁰³ and L¹⁰⁴, there are preferably illustrated asingle bond, an alkylene group, an alkenylene group, an oxygenatom-linking group, an amino-linking group, and an imino-linking group,more preferably a single bond, an alkylene linking group, an alkenylenelinking group, and an imino-linking group, and furthermore preferably asingle bond and an alkylene linking group.

Q¹⁰¹ and Q¹⁰³ each represent a group containing a carbon, nitrogen,phosphorus, oxygen or sulfur atom as a coordinating atom to M¹⁰¹respectively.

As the group containing a carbon atom as the coordinating atom, thereare preferably illustrated an aryl group, a 5-membered hetero arylgroup, and a 6-membered hetero aryl group, each containing a carbon atomas the coordinating atom, more preferably an aryl group, a 5-memberednitrogen-containing hetero aryl group, and a 6-memberednitrogen-containing hetero aryl group, each containing a carbon atom asthe coordinating atom, and furthermore preferably an aryl groupcontaining a carbon atom as the coordinating atom.

As the group containing a nitrogen atom as the coordinating atom, thereare preferably illustrated a 5-membered nitrogen-containing hetero arylgroup, and a 6-membered nitrogen-containing hetero aryl group, eachcontaining a nitrogen atom as the coordinating atom, and more preferablya 6-membered nitrogen-containing hetero aryl group containing a nitrogenatom as the coordinating atom.

As the group containing a phosphorus atom as the coordinating atom,there are preferably illustrated an alkylphosphine group, anarylphosphine group, an alkoxyphosphine group, an aryloxyphosphinegroup, a hetero aryloxyphosphine group, a phosphinine group, and aphosphole group, each containing a phosphorus atom as the coordinatingatom, and more preferably an alkylphosphine group, and an arylphosphinegroup, each containing a phosphorus atom as the coordinating atom.

As the group containing a oxygen atom as the coordinating atom, thereare preferably illustrated an oxy group, and a carboxyl group containingan oxygen atom as the coordinating atom, and more preferably an oxygroup.

As the group containing a sulfur atom as the coordinating atom, thereare preferably illustrated a sulfido group, a thiophene group, and athiazole group, and more preferably a thiophene group.

Q¹⁰¹ and Q¹⁰³ each preferably represent a group containing a carbon,nitrogen, or oxygen atom as a coordinating atom to M¹⁰¹ respectively;more preferably a group containing a carbon or nitrogen atom as thecoordinating atom; and further preferably a group containing a carbonatom as the coordinating atom.

Q¹⁰² represents a group containing a nitrogen, phosphorus, oxygen orsulfur atom as a coordinating atom to M¹⁰¹ respectively. The groupcontaining a nitrogen atom as the coordinating atom is more preferableas Q¹⁰².

M¹⁰¹ has the same meaning as that of the aforementioned M¹¹, with thesame preferable range.

Next, the compound represented by formula (15) will be described.

Z⁵⁰¹, Z⁵⁰², Z⁵⁰³, L⁵⁰¹, L⁵⁰², L⁵⁰³, L⁵⁰⁴, Q⁵⁰¹, Q⁵⁰², Q⁵⁰³, and M⁵⁰¹have the same meanings as those of the aforementioned Z¹⁰¹, Z¹⁰², Z¹⁰³,L¹⁰¹, L¹⁰², L¹⁰³, L¹⁰⁴, Q¹⁰¹, Q¹⁰³, Q¹⁰², and M¹⁰¹, respectively, withthe same preferable ranges.

Next, the compound represented by formula (12) will be described.

Z²⁰¹, Z²⁰², Z²⁰³, Z²⁰⁷, Z²⁰⁸, Z²⁰⁹, L²⁰¹, L²⁰², L²⁰³, L²⁰⁴, and M²⁰¹have the same meanings as those of the aforementioned Z¹⁰¹, Z¹⁰², Z¹⁰³,Z¹⁰¹, Z¹⁰², Z¹⁰³, L¹⁰¹, L¹⁰², L¹⁰³, L¹⁰⁴, and M¹⁰¹, respectively, withthe same preferable ranges. Z²⁰⁴, Z²⁰⁵, Z²⁰⁶, Z²¹⁰, Z²¹¹ and Z²¹² eachrepresent a substituted or unsubstituted carbon atom or nitrogen atom,with a substituted or unsubstituted carbon atom being preferable.

A combination of L²⁰¹, L²⁰², L²⁰³ and L²⁰⁴ is preferably that L²⁰¹,L²⁰², L²⁰³ and L²⁰⁴ each are an alkylene group; and more preferably thatL²⁰¹ and L²⁰³ each are a single bond, and L²⁰² and L²⁰⁴ each are analkylene group. A combination of Z²⁰⁴, Z²⁰⁶, Z²¹⁰ and Z²¹² is preferablythat at least one of Z²⁰⁴, Z²⁰⁶, Z²¹⁰ and Z²¹² is a carbon atomsubstituted with a fluorine atom; and more preferably that Z²⁰⁴, Z²⁰⁶,Z²¹⁰ and Z²¹² each are a carbon atom substituted with a fluorine atom.It is preferable that Z²⁰² and Z²⁰⁸ each independently are a carbon atomsubstituted with any of an alkyl group, alkoxy group or dialkylaminogroup.

Next, the compound represented by formula (13) will be described.

Z³⁰¹, Z³⁰², Z³⁰³, Z³⁰⁴, Z³⁰⁵, Z³⁰⁶, Z³⁰⁷, Z³⁰⁸, Z³⁰⁹, Z³¹⁰, L³⁰¹, L³⁰²,L³⁰³, L³⁰⁴, and M³⁰¹ have the same meanings as those of theaforementioned Z²⁰¹, Z²⁰², Z²⁰³, Z²⁰⁴, Z²⁰⁶, Z²⁰⁷, Z²⁰⁸, Z²⁰⁹, Z²¹⁰,Z²¹², L¹⁰¹, L¹⁰², L¹⁰³, L¹⁰⁴, and M¹⁰¹, respectively, with the samepreferable ranges.

A combination of L³⁰¹, L³⁰², L³⁰³ and L³⁰⁴ is preferably that L³⁰¹,L³⁰², L³⁰³ and L³⁰⁴ each are an alkylene group; and more preferably thatL³⁰¹ and L³⁰³ each are a single bond, and L³⁰² and L³⁰⁴ each are analkylene group. A combination of Z³⁰⁴, Z³⁰⁵, Z³⁰⁹ and Z³¹⁰ is preferablythat at least two of Z³⁰⁴, Z³⁰⁵, Z³⁰⁹ and Z³¹⁰ are each a nitrogen atom.It is preferable that Z³⁰² and Z³⁰⁷ each independently are a carbon atomsubstituted with any of an alkyl group, alkoxy group or dialkylaminogroup.

Next, the compound represented by formula (14) will be described.

Z⁴⁰¹, Z⁴⁰², Z⁴⁰³, Z⁴⁰⁴, Z⁴⁰⁵, Z⁴⁰⁶, Z⁴⁰⁷, Z⁴⁰⁸, Z⁴⁰⁹, Z⁴¹⁰, Z⁴¹¹, Z⁴¹²,L⁴⁰¹, L⁴⁰², L⁴⁰³, L⁴⁰⁴, and M⁴⁰¹ have the same meanings as those of theaforementioned Z²⁰¹, Z²⁰², Z²⁰³, Z²⁰⁴, Z²⁰⁵, Z²⁰⁶, Z²⁰⁷, Z²⁰⁸, Z²⁰⁹,Z²¹⁰, Z²¹¹, Z²¹², L¹⁰¹, L¹⁰², L¹⁰³, L¹⁰⁴, and M¹⁰¹, respectively, withthe same preferable ranges.

X⁴⁰¹ and X⁴⁰² each represent an oxygen atom, a substituted orunsubstituted nitrogen atom, or a sulfur atom, preferably an oxygen atomor a substituted nitrogen atom, and more preferably an oxygen atom.

A combination of L⁴⁰¹, L⁴⁰², L⁴⁰³ and L⁴⁰⁴ is preferably that L⁴⁰¹,L⁴⁰², L⁴⁰³ and L⁴⁰⁴ each are an alkylene group; and more preferably thatL⁴⁰¹ and L⁴⁰³ each are a single bond, and L⁴⁰² and L⁴⁰⁴ each are analkylene group. A combination of Z⁴⁰⁴, Z⁴⁰⁶, Z⁴¹⁰ and Z⁴¹² is preferablythat at least one of Z⁴⁰⁴, Z⁴⁰⁶, Z⁴¹⁰ and Z⁴¹² is a carbon atomsubstituted with a fluorine atom; and more preferably that Z⁴⁰⁴, Z⁴⁰⁶,Z⁴¹⁰ and Z⁴¹² each are a carbon atom substituted with a fluorine atom.It is preferable that Z⁴⁰² and Z⁴⁰⁸ each independently are a carbon atomsubstituted with any of an alkyl group, alkoxy group or dialkylaminogroup.

Next, the compound represented by formula (16) will be described.

Z⁶⁰¹, Z⁶⁰², Z⁶⁰³, Z⁶⁰⁴, Z⁶⁰⁵, Z⁶⁰⁶, Z⁶⁰⁷, Z⁶⁰⁸, Z⁶⁰⁹, Z⁶¹⁰, Z⁶¹¹, Z⁶¹²,L⁶⁰¹, L⁶⁰², L⁶⁰³, L⁶⁰⁴, and M⁶⁰¹ have the same meanings as those of theaforementioned Z²⁰¹, Z²⁰², Z²⁰³, Z²⁰⁷, Z²⁰⁸, Z²⁰⁹, Z²⁰⁴, Z²⁰⁵, Z²⁰⁶,Z²¹⁰, Z²¹¹, Z²¹², L¹⁰¹, L¹⁰², L¹⁰³, L¹⁰⁴, and M¹⁰¹, respectively, withthe same preferable ranges.

A combination of L⁶⁰¹, L⁶⁰², L⁶⁰³ and L⁶⁰⁴ is preferably that L⁶⁰¹,L⁶⁰², L⁶⁰³ and L⁶⁰⁴ each are an alkylene group; and more preferably thatL⁶⁰¹ and L⁶⁰³ each are a single bond, and L⁶⁰² and L⁶⁰⁴ each are analkylene group. A combination of Z⁶⁰⁷, Z⁶⁰⁹, Z⁶¹⁰ and Z⁶¹² is preferablythat at least one of Z⁶⁰⁷, Z⁶⁰⁹, Z⁶¹⁰ and Z⁶¹² is a carbon atomsubstituted with a fluorine atom; and more preferably that Z⁶⁰⁷, Z⁶⁰⁹,Z⁶¹⁰ and Z⁶¹² each are a carbon atom substituted with a fluorine atom.It is preferable that Z⁶⁰² and Z⁶⁰⁵ each independently are a carbon atomsubstituted with any of an alkyl group, alkoxy group or dialkylaminogroup.

Next, the compound represented by formula (17) will be described.

Z⁷⁰¹, Z⁷⁰², Z⁷⁰³, Z⁷⁰⁴, Z⁷⁰⁵, Z⁷⁰⁶, Z⁷⁰⁷, Z⁷⁰⁸, Z⁷⁰⁹, Z⁷¹⁰, L⁷⁰¹, L⁷⁰²,L⁷⁰³, L⁷⁰⁴, and M⁷⁰¹ have the same meanings as those of theaforementioned Z²⁰¹, Z²⁰², Z²⁰³, Z²⁰⁷, Z²⁰⁸, Z²⁰⁹, Z²⁰⁴, Z²⁰⁶, Z²¹⁰,Z²¹², L¹⁰¹, L¹⁰², L¹⁰³, L¹⁰⁴, and M¹⁰¹, respectively, with the samepreferable ranges.

A combination of L⁷⁰¹, L⁷⁰², L⁷⁰³ and L⁷⁰⁴ is preferably that L⁷⁰¹,L⁷⁰², L⁷⁰³ and L⁷⁰⁴ each are an alkylene group; and more preferably thatL⁷⁰¹ and L⁷⁰³ each are a single bond, and L⁷⁰² and L⁷⁰⁴ each are analkylene group. A combination of Z⁷⁰⁷, Z⁷⁰⁸, Z⁷⁰⁹ and Z⁷¹⁰ is preferablythat at least two of Z⁷⁰⁷, Z⁷⁰⁸, Z⁷⁰⁹ and Z⁷¹⁰ are each a nitrogen atom.It is preferable that Z⁷⁰² and Z⁷⁰⁵ each independently are a carbon atomsubstituted with any of an alkyl, group, alkoxy group or dialkylaminogroup.

Next, the compound represented by formula (18) will be described.

Z⁸⁰¹, Z⁸⁰², Z⁸⁰³, Z⁸⁰⁴, Z⁸⁰⁵, Z⁸⁰⁶, Z⁸⁰⁷, Z⁸⁰⁸, Z⁸⁰⁹, Z⁸¹⁰, Z⁸¹¹, Z⁸¹²,L⁸⁰¹, L⁸⁰², L⁸⁰³, L⁸⁰⁴, M⁸⁰¹, X⁸⁰¹ and X⁸⁰² have the same meanings asthose of the aforementioned Z²⁰¹, Z²⁰², Z²⁰³, Z²⁰⁷, Z²⁰⁸, Z²⁰⁹, Z²⁰⁴,Z²⁰⁵, Z²⁰⁶, Z²¹⁰, Z²¹¹, Z²¹², L¹⁰¹, L¹⁰², L¹⁰³, L¹⁰⁴, M¹⁰¹, X⁴⁰¹ andX⁴⁰² respectively, with the same preferable ranges.

A combination of L⁸⁰¹, L⁸⁰², L⁸⁰³ and L⁸⁰⁴ is preferably that L⁸⁰¹,L⁸⁰², L⁸⁰³ and L⁸⁰⁴ each are an alkylene group; and more preferably thatL⁸⁰¹ and L⁸⁰³ each are a single bond, and L⁸⁰² and L⁸⁰⁴ each are analkylene group. A combination of Z⁸⁰⁷, Z⁸⁰⁹, Z⁸¹⁰ and Z⁸¹² is preferablythat at least one of Z⁸⁰⁷, Z⁸⁰⁹, Z⁸¹⁰ and Z⁸¹² is a carbon atomsubstituted with a fluorine atom; and more preferably that Z⁸⁰⁷, Z⁸⁰⁹,Z⁸¹⁰ and Z⁸¹² each are a carbon atom substituted with a fluorine atom.It is preferable that Z⁸⁰² and Z⁸⁰⁵ each independently are a carbon atomsubstituted with any of an alkyl group, alkoxy group or dialkylaminogroup.

The compound of the present invention may be a low molecular compound,or may be an oligomer compound or a polymer compound having aweight-average molecular weight calculated in terms of polystyrenepreferably in the range of 1,000 to 5,000,000, more preferably in therange of 2,000 to 1,000,000, and furthermore preferably in the range of3,000 to 100,000. With respect to the polymer compound, the structurerepresented, for example, by formula (1) may be contained in a mainchain of the polymer, or in a side chain of the polymer. Further, thepolymer compound may be a homopolymer or a copolymer. The compound ofthe present invention is preferably a low molecular compound.

Specific examples of the compound of the present invention are shownbelow, but the present invention is not limited to these compounds.

The compounds of the present invention that are represented by formula(1) can be synthesized according to, for example, the method describedin Journal of Chemical Society, 5008 (1952), or synthesis methodsdescribed below.

The compounds of the present invention that are represented by formula(1) (n¹¹=1) can be synthesized according to various methods. Forexample, the compounds can be obtained by reacting a ligand or itsdissociated product with a compound containing M¹¹, in the presence of asolvent (e.g., a halogen-series solvent, an alcohol-series solvent, anether-series solvent, an ester-series solvent, a ketone-series solvent,a nitrile-series solvent, an amide-series solvent, a sulfone-seriessolvent, a sulfoxide-series solvent and water), or in the absence of asolvent, in the presence of a base (various inorganic or organic bases,such as sodium methoxide, potassium t-butoxide, triethylamine andpotassium carbonate), or in the absence of a base, at room temperatureor below, or alternatively by heating (in addition to an ordinaryheating, a method of heating by means of microwave is also effective).

A reaction time that is applied in synthesizing the compound of thepresent invention that is represented by formula (1) (n¹¹=1) from acompound containing M¹¹ varies depending upon reaction activity, andthere is no particular limitation as to the reaction time, butpreferably the reaction time is in the range of from 1 minute to 5 days,more preferably in the range of from 5 minutes to 3 days, andfurthermore preferably in the range of from 10 minutes to 1 day.

A reaction temperature that is applied in synthesizing the compound ofthe present invention that is represented by formula (1) (n¹¹=1) from acompound containing M¹¹ varies depending upon reaction activity, andthere is no particular limitation as to the reaction temperature, butthe reaction temperature is preferably in the range of from 0° C. to300° C., more preferably in the range of from 5° C. to 250° C., andfurthermore preferably in the range of from 10° C. to 200° C.

The compound of the present invention that is represented by formula (1)(n¹¹=1) can be synthesized by adding a ligand that has a partialstructure of an objective complex (for example, Compound (I) insynthesis of Compound (8)) preferably in an equivalent amount of from0.1 to 10, more preferably in an equivalent amount of from 0.3 to 6,furthermore preferably in an equivalent amount of from 0.5 to 4, to ametal compound respectively. As the aforementioned metal compound, thereare illustrated a metal halide (e.g., platinum chloride), a metalacetate (e.g., palladium acetate), an acetylacetonato-metal (e.g.,acetylacetonatoeuropium), and hydrates of these compounds. The compoundsof the present invention that are represented by formula (6) can beobtained by reacting a ligand that has a partial structure of formula(6) (e.g., Compound (1), Compound (9), Compound (14), Compound (21),Compound (24)) with a platinum compound (e.g., PtCl₂, K₂PtCl₄,Pt(acac)₂). The compound represented by formula (1) (n¹¹=1) also can besynthesized in the same manner as the compound represented by formula(6). The compounds of the present invention that are represented byformula (6) can be synthesized according to the aforementioned synthesismethod of the compound represented by formula (1).

Next, luminescent devices containing a compound of the present inventionare explained below.

The luminescent devices of the present invention can employ ordinaryluminescent systems, driving methods and using forms, provided that thedevice uses the compound of the present invention. The compoundrepresented, for example, by formula (1) is preferably used as aluminescent material, or a hole injection material/hole-transportingmaterial. The luminescent material to be used may be ultravioletemission or infrared emission, or fluorescence emission orphosphorescence emission. As a typical luminescent device, there areorganic EL (electroluminescence) devices.

Optical output efficiency of the luminescent device of the presentinvention can be improved according to various known methods. Forexample, the optical output efficiency can be improved by processing asurface shape of the substrate (for example, formation of fine unevenpattern), controlling refractive indices among a substrate, an ITO layerand an organic layer(s), or controlling thickness among a substrate, anITO layer and an organic layer(s). Thereby external quantum efficiencycan be improved.

The luminescent device of the present invention may be a so-called topemission system of the device that output light emission from thepositive electrode side, as described in, for example, JP-A-2003-208109,JPA-2003-248441, JP-A-2003-257651 and JP-A-2003-282261.

The substrate that can be used in the luminescent device of the presentinvention is not particularly restricted. Examples of the substrateinclude inorganic materials, such as zirconia-stabilized yttrium, andglass; polyesters, such as polyethylene terephthalate, polybutyleneterephthalate and polyethylene naphthalate; and high molecular weightmaterials, such as polyethylene, polycarbonate, polyethersulfone,polyarylate, allyldiglycolcarbonate, polyimide, polycycloolefin,norbornene resin, poly(chlorotrifluoroethylene), polytetrafluoroethylene(Teflon (registered trade mark)), andpolytetrafluoroethylene/polyethylene copolymers.

The organic electroluminescent device of the present invention maycontain a blue-fluorescent compound. Alternatively, a blue luminescentdevice containing a blue fluorescent compound and the luminescent deviceof the present invention may be used together, to prepare a multicolorlight-emitting device or a full color light-emitting device.

The host material for use in the luminescent device of the presentinvention may be of one kind, or of two or more kinds. As the hostmaterial, are preferable arylamine derivatives (for example,triphenylamine derivatives, benzidine derivatives), aromatic hydrocarboncompounds (for example, triphenylbenzene derivatives, triphenylenederivatives, phenanthrene derivatives, naphthalene derivatives,tetraphenylene derivatives), aromatic nitrogen-containing heterocycliccompounds (for example, pyridine derivatives, pyrazine derivatives,pyrimidine derivatives, triazine derivatives, pyrazole derivatives,imidazole derivatives, oxazole derivatives, pyrrole derivatives), andmetal complexes (for example, zinc complexes, aluminum complexes,gallium complexes).

The electroluminescent device of the present invention preferably has,between a negative electrode and a luminescent layer, a layer containinga compound having ionization potential of 5.9 eV or more (morepreferably 6.0 eV or more), and more preferably has anelectron-transporting layer having ionization potential of 5.9 eV ormore.

A method of forming an organic layer of the luminescent devicecontaining the compound of the present invention is not particularlylimited. As the method, various methods, such as a resistanceheating-utilizing vapor deposition method, an electron-beam method, asputtering method, a molecular lamination method, a coating method(e.g., a splay coating method, dip coating method, dipping method, rollcoating method, gravure coating method, reverse coating method, rollbrushing method, air knife coating method, curtain coating method, spincoating method, flow coating method, bar coating method, micro gravurecoating method, air doctor coating method, blade coating method, squeezecoating method, transfer roll coating method, kiss coating method, castcoating method, extrusion coating method, wire bar coating method andscreen coating method), an inkjet method, a printing method, and atransfer method, can be adopted. From the viewpoints of characteristicsand production, a resistance heating-utilized vapor deposition method, acoating method and a transfer method are preferable. A layer of thecompound of the present invention may be formed on a substrate,according to any one of the aforementioned forming methods. The layerhas no particular limitation as to its thickness, but the layerthickness is preferably 10 nm or more, and more preferably in the rangeof from 50 nm to 5 μm.

The luminescent device of the present invention is a device having aluminescent layer or at least two thin film layers of organic compoundsincluding a luminescent layer formed between a pair of electrodes, apositive electrode (anode) and a negative electrode (cathode). Examplesof the thin layer(s) that the luminescent device may have in addition tothe luminescent layer, include a hole injection layer, ahole-transporting layer, an electron injection layer, anelectron-transporting layer, a protective layer, and the like. Further,these layers each may have other functions. For forming each layer,various kinds of materials may be used.

The positive electrode is to supply positive holes to a positivehole-injecting layer, a positive hole-transporting layer, a luminescentlayer, and the like, and metals, alloys, metal oxides, electricallyconductive compounds, or mixtures of these can be used therefor,materials having a work function of 4 eV or more are preferably used.Specific examples of the materials include electrically conductive metaloxides, such as tin oxide, zinc oxide, indium oxide, and indium tinoxide (ITO); metals, such as gold, silver, chromium, and nickel;mixtures or laminations of these metals with electrically conductivemetal oxides; inorganic electrically conductive substances, such ascopper iodide and copper sulfide; organic electrically conductivesubstances, such as polyaniline, polythiophene, and polypyrrole; andlaminations of these materials with ITO. Electrically conductive metaloxides are preferably used, and ITO is particularly preferably used inview of producibility, high conductivity and transparency. The filmthickness of the positive electrode can be selected arbitrarilyaccording to materials to be used, but is generally preferably from 10nm to 5 nm, more preferably from 50 nm to 1 nm, and still morepreferably from 100 nm to 500 nm.

The positive electrode generally comprises a layer(s) formed on asoda-lime glass, non-alkali glass or transparent resin substrate. When aglass substrate is used, non-alkali glass is preferably used forlessening elution of ions from the glass. Further, when soda-lime glassis used, it is preferred to provide a barrier coat such as silica. Thethickness of the substrate is not particularly limited so long as it cansufficiently stand mechanical strength. When glass is used, thethickness is generally 0.2 mm or more, preferably 0.7 mm or more.

Various processes are used in the manufacture of the positive electrodeaccording to the materials to be used. In the case of using ITO, forexample, a thin layer film(s) is formed by an electron beam process, asputtering process, a resistance heating vapor deposition process, achemical reaction process (e.g. a sol-gel process), or the process ofcoating a dispersion of an indium tin oxide.

It is possible to reduce the driving voltage or increase the luminescentefficacy of the device or element, by the process such as washing of thepositive electrode. In the case of using ITO, for example, UV-ozoneprocessing or plasma treatment is effective.

The negative electrode is to supply electrons to an electron-injectinglayer, an electron-transporting layer, a luminescent layer, and thelike, and the negative electrode is selected taking into considerationthe adhesion with the layer adjacent to the negative electrode, such asan electron-injecting layer, electron-transporting layer, or luminescentlayer; ionization potential, and stability. As materials of the negativeelectrode, metals, alloys, metal halides, metal oxides, electricallyconductive compounds, or mixtures of these materials can be used.Specific examples include alkali metals (e.g., Li, Na, K) or theirfluorides or oxides, alkaline earth metals (e.g., Mg, Ca) or theirfluorides or oxides, gold, silver, lead, aluminum, sodium-potassiumalloys or mixed metals thereof, lithium-aluminum alloys or mixed metalsthereof, magnesium-silver alloys or mixed metals thereof, and rare earthmetals, such as indium, ytterbium, and the like; preferably materialshaving a work function of 4 eV or less, and more preferably aluminum,lithium-aluminum alloys or mixed metals thereof, and magnesium-silveralloys or mixed metals thereof. The negative electrode structure may benot only a single layer of the aforementioned compound or mixturethereof, but also a laminate comprised of the aforementioned compound ormixture thereof. For example, laminate structures of aluminum/lithiumfluoride, or aluminum/lithium oxide are preferable. The film thicknessof the negative electrode can be selected arbitrarily according tomaterials to be used, but is generally preferably from 10 nm to 5 μm,more preferably from 50 nm to 1 μm, and still more preferably from 100nm to 1 μm.

Processes such as an electron beam process, a sputtering process, aresistance heating vapor deposition process, a coating process, and atransfer method are used in the manufacture of the negative electrode,and a single metal can be vapor-deposited or two or more components canbe vapor-deposited at the same time. Further, a plurality of metals canbe vapor-deposited at the same time to form an alloy electrode,alternatively a previously prepared alloy can be vapor-deposited.

It is preferred that the sheet resistance of the positive electrode andthe negative electrode be low, preferably several hundreds Ω/□ or less.

The material for a luminescent layer may be any of materials capable offorming a layer that can function so as to accept both injection ofholes from the positive electrode, the hole injection layer or thehole-transporting layer and injection of electrons from the negativeelectrode, the electron injection layer or the electron-transportinglayer when electric field is applied thereto, or to let the chargesinjected therein to transfer, or to enable the emission of light byproviding a cite for recombining the holes and the electrons. Besidesthe compound of the present invention, examples of the material includevarious metal complexes typically exemplified by metal complex or rareearth complex of benzoxazole derivatives, benzimidazole derivatives,benzothiazole derivatives, styrylbenzene derivatives, polyphenylderivatives, diphenylbutadiene derivatives, tetraphenylbutadienederivatives, naphthalimide derivatives, coumarin derivatives, perylenederivatives, perinone derivatives, oxadiazole derivatives, aldazinederivatives, pyraridine derivatives, cyclopentadiene derivatives,bisstyrylanthracene derivatives, quinacridone derivatives,pyrrolopyridine derivatives, thiadiazolopyridine derivatives,cyclopentadiene derivatives, styrylamine derivatives, aromaticdimethylidyne compounds, and 8-quinolinol derivatives; polymericcompounds, such as polythiophene, polyphenylene, andpolyphenylenevinylene; organic silanes; transition metal complexes(e.g., iridium trisphenylpyridine and platinum porphyrin, andderivatives thereof). The film thickness of the luminescent layer is notparticularly restricted, but it is generally preferably from 1 nm to 5mm, more preferably from 5 nm to 1 μm, and still more preferably from 10nm to 500 nm.

Although there is no particular limitation on methods for forming theluminescent (light emitting) layers, methods such as resistance heatingvapor deposition, electron beam processing, sputtering, molecularlamination, coating, inkjet process, printing, LB processing, andtransfer process can be used. Preferred are a resistance heating vapordeposition method and a coating method.

The luminescent layer may be formed of a single compound, or two or morekinds of compounds. Further, the luminescent layer may have a singlelayer structure, or a multiple-layer structure made of at least twolayers. Each layer may emit light of a different luminescent color sothat the luminescent layer can emit, for example, a white light. Asingle luminescent layer may emit a white light. When the luminescentlayer is a plurality of layers, each layer may be formed of a singlematerial, or at least two compounds or materials.

Materials of the positive hole-injecting layer and the positivehole-transporting layer are sufficient if they have any of the functionsof injecting positive holes from the positive electrode, transportingpositive holes, and blocking the electrons injected from the negativeelectrode. Specific examples of the materials include carbazolederivatives, triazole derivatives, oxazole derivatives, oxadiazolederivatives, imidazole derivatives, polyarylalkane derivatives,pyrazoline derivatives, pyrazolone derivatives, phenylenediaminederivatives, arylamine derivatives, amino-substituted chalconederivatives, styrylanthracene derivatives, fluorenone derivatives,hydrazone derivatives, stilbene derivatives, silazane derivatives,aromatic tertiary amine compounds, styrylamine compounds, aromaticdimethylidyne-series compounds, porphyrin-series compounds,polysilane-series compounds, poly(N-vinylcarbazole) derivatives,aniline-series copolymers, electrically conductive high molecular weightoligomers, such as thiophene oligomers and polythiophene; organic silanecompounds, carbon film, and the compounds of the present invention. Thefilm thickness of the hole-injection layer is not particularly limited,and in general, it is preferably from 1 nm to 5 μm, more preferably from1 nm to 100 nm, and further preferably from 1 nm to 10 nm. The filmthickness of the hole-transporting layer is not particularly limited,and in general, it is preferably from 1 nm to 5 μm, more preferably from5 nm to 1 μm, and further preferably from 10 nm to 500 nm. Thehole-injecting layer or hole-transporting layer may have a single layerstructure of one kind or two or more kinds of the above materials, oralternatively, a multilayer structure comprising plural layers havingthe same composition or different compositions.

Examples of a method of forming the hole-injecting layer and thehole-transporting layer include a vacuum deposition method, an LBmethod, the process of dissolving or dispersing the above-describedhole-injecting/transporting material in a solvent and coating; an inkjet method, a printing method, and a transfer method. In the case of acoating process, a positive hole-injecting/transporting material can bedissolved or dispersed with a resin component. Examples of such resincomponents include polyvinyl chloride, polycarbonate, polystyrene,polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone,polyphenylene oxide, polybutadiene, poly(N-vinylcarbazole), hydrocarbonresin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinylacetate, ABS resin, polyurethane, melamine resin, unsaturated polyesterresin, alkyd resin, epoxy resin, silicone resin, and the like.

Materials of the electron-injecting layer and the electron-transportinglayer are sufficient if they have any of the functions of injectingelectrons from the negative electrode, transporting electrons, andblocking (as a barrier off) the positive holes injected from thepositive electrode. Specific examples of the materials include triazolederivatives, oxazole derivatives, oxadiazole derivatives, imidazolederivatives, fluorenone derivatives, anthraquinodimethane derivatives,anthrone derivatives, diphenylquinone derivatives, thiopyrandioxidederivatives, carbodiimide derivatives, fluorenylidenemethanederivatives, distyrylpyrazine derivatives, tetracarboxylic acidanhydrides of aromatic rings such as naphthalene and perylene,phthalocyanine derivatives, various metal complexes represented by metalcomplexes of 8-quinolinol derivatives, metallophthalocyanines and metalcomplexes having benzoxazole or benzothiazole ligands, organosilanecompounds. The film thickness of the electron-injecting layer and theelectron-transporting layer is not particularly restricted, but it isgenerally preferably from 1 nm to 5 μm, more preferably from 5 nm to 1μm, and still more preferably from 10 nm to 500 nm. Theelectron-injecting layer and the electron-transporting layer may besingle layer structure comprising one or two or more of the abovematerials, or may be multilayer structure comprising a plurality oflayers of the same composition or different compositions.

Examples of a method of forming the electron injecting layer and theelectron transporting layer include a vacuum deposition method, an LBmethod, the process of dissolving or dispersing the above-describedelectron-injecting/transporting material in a solvent and coating; anink jet method, a printing method, and a transfer method. In the case ofa coating process, an electron injecting/transporting material can bedissolved or dispersed with a resin component. As the resin components,for example, those exemplified in the positive hole-injecting andtransporting layers can be applied.

Materials of the protective layer are sufficient if they have thefunction of preventing substances which accelerate deterioration of thedevice or element, such as water or oxygen, from entering the device orelement. Specific examples of the materials include metals such as In,Sn, Pb, Au, Cu, Ag, Al, Ti and Ni; metal oxides such as MgO, SiO, SiO₂,Al₂O₃, GeO, NiO, CaO, BaO, Fe₂O₃, Y₂O₃ and TiO₂; metal fluorides such asMgF₂, LiF, AlF₃ and CaF₂; metal nitrides such as SiN_(x) andSiO_(x)N_(y); polyethylene, polypropylene, polymethyl methacrylate,polyimide, polyurea, polytetrafluoroethylene,polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymers ofchlorotrifluoroethylene and dichlorodifluoroethylene, copolymersprepared by copolymerizing a monomer mixture of tetrafluoroethylene andat least one comonomer, fluorine-containing copolymers having cyclicstructures on the main chain, water-absorbing substances having a waterabsorption rate of at least 1%, and moisture-proof substances having awater absorption rate of at most 0.1%.

The forming process of the protective layer is also not particularlyrestricted, and, for example, a vacuum deposition process, a sputteringprocess, a reactive sputtering process, an MBE (molecular beam epitaxy)process, a cluster ion beam process, an ion-plating process, a plasmapolymerization process (a high frequency exciting ion-plating process),a plasma CVD process, a laser CVD process, a heat CVD process, a gassource CVD process, a coating process, a printing process, and atransfer process can be applied.

The luminescent device of the present invention is excellent inluminescent properties and long in life. Further, the novel platinumcompound of the present invention is preferable, for example, forproducing the luminescent device.

EXAMPLES

The present invention will be explained in more detail with reference tothe examples below, but the embodiments for carrying out the presentinvention should not be construed to be limited to these.

Synthesis of Compound (1)

Compound (1) was synthesized, according to the method described inJournal of Chemical Society, 5008 (1952). That is, 40 ml of n-butanolwas added to 6 g of 1,3-diiminoindoline and 4.6 g of2,6-diaminopyridine, followed by heating under reflux for 9 hours. Aftercooling to room temperature, the reaction mixture was filtered. Theprecipitate was washed with 40 ml of n-butanol and dispersed in 50 ml ofnitrobenzene. After the dispersion was heated under reflux,recrystallization was conducted by cooling, to yield 7 g of Compound(I).

With respect to the thus-obtained compound, a peak of m/z=440 wasdetected in DP-EI-MS measurement.

Synthesis of Compound (8)

To 0.1 g of Compound (I) and 0.21 g of PtCl₂, 10 ml of benzonitrile wasadded, followed by stirring, at an inner temperature of 160° C. under anitrogen atmosphere, for 4 hours. After cooling to room temperature, thereaction mixture was filtered. The precipitate was washed with 20 ml ofbenzonitrile and 30 ml of methanol, to yield 0.05 g of Compound (8).

With respect to the thus-obtained compound, a peak of m/z=633 wasdetected in DP-EI-MS measurement.

Comparative Example 1

A cleaned ITO substrate was placed in a vapor deposition apparatus, andon the substrate, CuPc (copper phthalocyanine) was vapor-deposited, toform a film of 10 nm thickness, and then α-NPD(4,4′-bis-[N-(1-naphthyl)-N-phenylamino]biphenyl) was vapor-deposited,to form a film of 40 nm thickness, and then Alq₃(tris(8-hydroxyquinolinato)aluminum complex) was vapor-deposited, toform a film of 60 nm thickness, in this order. Then, a patterned mask(for adjusting each emission area to 4 mm×5 mm) was set on theabove-obtained organic thin layers, and further thereon, in the vacuumdeposition apparatus, lithium fluoride was vapor-deposited, to form afilm of 3 nm thickness, followed by vapor-deposition of a 400 nm-thickAl film. The thus-produced EL device was subjected to luminescence byapplying, thereto, a DC constant voltage, by means of a source measureunit, Model 2400 (trade name), made by Toyo Technica Co., Ltd., and theluminance shown by the EL device was measured using a luminometer DM-8(trade name), made by Topcon Co. As a result of the measurement, thelight emission given by the EL device was found to be a greenluminescence of 200 cd/m² with quantum efficiency of 1.1%. After the ELdevice was subjected to luminescence of 100 cd/m² for 10 hours, darkspots were observed with the naked eye.

Example 1

A cleaned ITO substrate was placed in a vapor deposition apparatus, andon the substrate, Compound (8) of the present invention wasvapor-deposited, to form a film of 5 nm thickness, and then α-NPD(4,4′-bis-[N-(1-naphthyl)-N-phenylamino]biphenyl) was vapor-deposited,to form a film of 60 nm thickness, and then Alq₃(tris(8-hydroxyquinolinato)aluminum complex) was vapor-deposited, toform a film of 40 nm thickness, in this order. Then, a patterned mask(for adjusting each emission area to 4 mm×5 mm) was set on theabove-obtained organic thin layers, and further thereon, in the vacuumdeposition apparatus, lithium fluoride was vapor-deposited, to form afilm of 3 nm thickness, followed by vapor-deposition of a 400 nm-thickAl film. The thus-produced EL device was subjected to luminescence byapplying, thereto, a DC constant voltage, by means of a source measureunit, Model 2400, made by Toyo Technica Co., Ltd., and the luminanceshown by the EL device was measured using a luminometer BM-8, made byTopcon Co. As a result of the measurement, it was found that the ELdevice gave a green luminescence of 200 cd/m² with quantum efficiency of1.4%. After the EL device was subjected to luminescence of 100 cd/m² for10 hours, no dark spots were observed with the naked eye.

Similarly, by employing other compounds of the present invention,luminescent devices giving high luminous efficiency and long life canalso be produced. In addition, the compounds of the present inventionenable to emit a blue to green phosphorescence, and therefore blue togreen luminescent devices containing the compound of the presentinvention can be prepared.

INDUSTRIAL APPLICABILITY

The luminescent device of the present invention is able to give highluminous efficiency. The luminescent device of the present invention canbe preferably used in such fields as display devices, displays,backlights, electrophotography, illuminating light sources, recordinglight sources, exposing light sources, reading light sources, signs,signboards, interiors, and optical communications. Further, thecompounds of the present invention can be utilized for theelectroluminescent devices, as well as medical usage, brighteningagents, photographic materials, UV absorbing materials, laser dyes,recording media materials, inkjet pigments, color filter dyes, colorconversion filters, and the like.

Having described our invention as related to the present embodiments, itis our intention that the invention not be limited by any of the detailsof the description, unless otherwise specified, but rather be construedbroadly within its spirit and scope as set out in the accompanyingclaims.

1. An organic electroluminescent device, comprising a pair ofelectrodes, and at least one organic layer including a luminescent layerbetween the electrodes, wherein said organic layer comprises at leastone compound represented by formula (15):

wherein, in formula (15), Z⁵⁰¹, Z⁵⁰² and Z⁵⁰³ each represent asubstituted or unsubstituted carbon atom or nitrogen atom; L⁵⁰¹, L⁵⁰²,L⁵⁰³ and L⁵⁰⁴ each represent a single bond or a linking group; Q⁵⁰¹ andQ⁵⁰² each represent a group containing a carbon, nitrogen, phosphorus,oxygen or sulfur atom as a coordinating atom to M⁵⁰¹ respectively; Q⁵⁰³represents a group containing a nitrogen, phosphorus, oxygen or sulfuratom as a coordinating atom to M⁵⁰¹; and M⁵⁰¹ represents a metal ionthat may further have at least one ligand.
 2. An organicelectroluminescent device, comprising a pair of electrodes, and at leastone organic layer including a luminescent layer between the electrodes,wherein said organic layer comprises at least one compound representedby formula (5):

wherein, in formula (5), R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵ and R⁵⁶ each representa hydrogen atom or a substituent; X⁵¹, X⁵², X⁵³ and X⁵⁴ each represent asubstituted or unsubstituted carbon atom or nitrogen atom; Z⁵¹, Z⁵²,Z⁵³, Z⁵⁴, Z⁵⁵ and Z⁵⁶ each represent a substituted or unsubstitutedcarbon atom or nitrogen atom.
 3. The organic electroluminescent deviceas claimed in claim 1, wherein the compound represented by formula (15)is a compound represented by formula (16) or a tautomer thereof:

wherein, in formula (16), Z⁶⁰¹, Z⁶⁰², Z⁶⁰³, Z⁶⁰⁴, Z⁶⁰⁵, Z⁶⁰⁶, Z⁶⁰⁷,Z⁶⁰⁸, Z⁶⁰⁹, Z⁶¹⁰, Z⁶¹¹, and Z⁶¹² each represent a substituted orunsubstituted carbon atom or nitrogen atom; L⁶⁰¹, L⁶⁰², L⁶⁰³ and L⁶⁰⁴each represent a single bond or a linking group; and M⁶⁰¹ represents ametal ion that may further have at least one ligand.
 4. The organicelectroluminescent device as claimed in claim 1, wherein the compoundrepresented by formula (15) is a compound represented by formula (17) ora tautomer thereof:

wherein, in formula (17), Z⁷⁰¹, Z⁷⁰², Z⁷⁰³, Z⁷⁰⁴, Z⁷⁰⁵, Z⁷⁰⁶, Z⁷⁰⁷,Z⁷⁰⁸, Z⁷⁰⁹, and Z⁷¹⁰ each represent a substituted or unsubstitutedcarbon atom or nitrogen atom; L⁷⁰¹, L⁷⁰², L⁷⁰³ and L⁷⁰⁴ each represent asingle bond or a linking group; and M⁷⁰¹ represents a metal ion that mayfurther have at least one ligand.
 5. The organic electroluminescentdevice as claimed in claim 1, wherein the compound represented byformula (15) is a compound represented by formula (18) or a tautomerthereof:

wherein, in formula (18), Z⁸⁰¹, Z⁸⁰², Z⁸⁰³, Z⁸⁰⁴, Z⁸⁰⁵, Z⁸⁰⁶, Z⁸⁰⁷,Z⁸⁰⁸, Z⁸⁰⁹, Z⁸¹⁰, Z⁸¹¹, and Z⁸¹² each represent a substituted orunsubstituted carbon atom or nitrogen atom; L⁸⁰¹, L⁸⁰², L⁸⁰³ and L⁸⁰⁴each represent a single bond or a linking group; M⁸⁰¹ represents a metalion that may further have at least on ligand; and X⁸⁰¹ and X⁸⁰² eachrepresent an oxygen atom, a substituted or unsubstituted nitrogen atom,or a sulfur atom.